Zeolite SSZ-53

ABSTRACT

The present invention relates to a new crystalline zeolite SSZ-53 prepared by using phenylcycloalkylmethyl ammonium cations as structure directing agents.&lt;/PTEXT&gt;

This application is a continuation-in-part of Ser. No. 09/584,187, filedMay 31, 2000.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new crystalline zeolite SSZ-53, amethod for preparing SSZ-53 using a selected group ofphenylcycloalkyltrimethyl ammonium cations as templating agents, andprocesses employing SSZ-53 as a catalyst.

2. State of the Art

Because of their unique sieving characteristics, as well as theircatalytic properties, crystalline molecular sieves and zeolites areespecially useful in applications such as hydrocarbon conversion, gasdrying and separation. Although many different crystalline molecularsieves have been disclosed, there is a continuing need for new zeoliteswith desirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New zeolites may containnovel internal pore architectures, providing enhanced selectivities inthese processes.

Crystalline aluminosilicates are usually prepared from aqueous reactionmixtures containing alkali or alkaline earth metal oxides, silica, andalumina. Crystalline borosilicates are usually prepared under similarreaction conditions except that boron is used in place of aluminum. Byvarying the synthesis conditions and the composition of the reactionmixture, different zeolites can often be formed.

SUMMARY OF THE INVENTION

The present invention is directed to a family of crystalline molecularsieves with unique properties, referred to herein as “zeolite SSZ-53” orsimply “SSZ-53”. Preferably, SSZ-53 is obtained in its silicate,aluminosilicate, titanosilicate, vanadosilicate or borosilicate form.The term “silicate” refers to a zeolite having a high mole ratio ofsilicon oxide relative to aluminum oxide, preferably a mole ratiogreater than 400. As used herein, the term “aluminosilicate” refers to azeolite containing both alumina and silica and the term “borosilicate”refers to a zeolite containing oxides of both boron and silicon.

In accordance with this invention, there is also provided a zeolitehaving a mole ratio greater than about 20 of an oxide of a firsttetravalent element to an oxide of a second tetravalent elementdifferent from said first tetravalent element, trivalent element,pentavalent element or mixture thereof and having, after calcination,the X-ray diffraction lines of Table II.

Further, in accordance with this invention, there is provided a zeolitehaving a mole ratio greater than about 20 of an oxide selected fromsilicon oxide, germanium oxide and mixtures thereof to an oxide selectedfrom aluminum oxide, gallium oxide, iron oxide, boron oxide, titaniumoxide, indium oxide, vanadium oxide and mixtures thereof and having,after calcination, the X-ray diffraction lines of Table II below.

The present invention further provides such a zeolite having acomposition, as synthesized and in the anhydrous state, in terms of moleratios as follows:

YO₂/W_(c)O_(d) 20-150 M_(2/n)/YO₂ 0.01-0.03 Q/YO₂ 0.02-0.05

wherein Y is silicon, germanium or a mixture thereof; W is aluminum,gallium, iron, boron, titanium (potentially included as mixtures),indium, vanadium (potentially included as mixtures), or mixturesthereof; c is 1 or 2; d is 2 when c is 1 (i.e., W is tetravalent) or dis 3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when W ispentavalent); M is an alkali metal cation, alkaline earth metal cationor mixtures thereof; n is the valence of M (i.e., 1 or 2); and Q is atleast one phenylcycloalkylmethyl ammonium cation.

In accordance with this invention, there is also provided a zeoliteprepared by thermally treating a zeolite having a mole ratio of an oxideselected from silicon oxide, germanium oxide and mixtures thereof to anoxide selected from aluminum oxide, gallium oxide, iron oxide, boronoxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereofgreater than about 20 at a temperature of from about 200 C. to about 800C., the thus-prepared zeolite having the X-ray diffraction lines ofTable II. The present invention also includes this thus-prepared zeolitewhich is predominantly in the hydrogen form, which is prepared by ionexchanging with an acid or with a solution of an ammonium salt followedby a second calcination.

Also provided in accordance with the present invention is a method ofpreparing a crystalline material comprising an oxide of a firsttetravalent element and an oxide of a second tetravalent element whichis different from said first tetravalent element, trivalent element,pentavalent element or mixture thereof, said method comprisingcontacting under crystallization conditions sources of said oxides and atemplating agent comprising a phenylcycloalkylmethyl ammonium cation.

The present invention additionally provides a process for convertinghydrocarbons comprising contacting a hydrocarbonaceous feed athydrocarbon converting conditions with a catalyst comprising the zeoliteof this invention. The zeolite may be predominantly in the hydrogenform. It may also be substantially free of acidity.

Further provided by the present invention is a hydrocracking processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form.

This invention also includes a dewaxing process comprising contacting ahydrocarbon feedstock under dewaxing conditions with a catalystcomprising the zeolite of this invention, preferably predominantly inthe hydrogen form.

The present invention also includes a process for improving theviscosity index of a dewaxed product of waxy hydrocarbon feedscomprising contacting the waxy hydrocarbon feed under isomerizationdewaxing conditions with a catalyst comprising the zeolite of thisinvention, preferably predominantly in the hydrogen form.

The present invention further includes a process for producing a C₂₀+lube oil from a C₂₀+ olefin feed comprising isomerizing said olefin feedunder isomerization conditions over a catalyst comprising at least oneGroup VIII metal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

In accordance with this invention, there is also provided a process forcatalytically dewaxing a hydrocarbon oil feedstock boiling above about350 F. and containing straight chain and slightly branched chainhydrocarbons comprising contacting said hydrocarbon oil feedstock in thepresence of added hydrogen gas at a hydrogen pressure of about 15-3000psi with a catalyst comprising at least one Group VIII metal and thezeolite of this invention, preferably predominantly in the hydrogenform. The catalyst may be a layered catalyst comprising a first layercomprising at least one Group VIII metal and the zeolite of thisinvention, and a second layer comprising an aluminosilicate zeolitewhich is more shape selective than the zeolite of said first layer.

Also included in the present invention is a process for preparing alubricating oil which comprises hydrocracking in a hydrocracking zone ahydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400 F. and at apressure of from about 15 psig to about 3000 psig in the presence ofadded hydrogen gas with a catalyst comprising at least one Group VIIImetal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

Further included in this invention is a process for isomerizationdewaxing a raffinate comprising contacting said raffinate in thepresence of added hydrogen with a catalyst comprising at least one GroupVIII metal and the zeolite of this invention. The raffinate may bebright stock, and the zeolite may be predominantly in the hydrogen form.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content comprising contacting a hydrocarbonaceous feedstockwhich comprises normal and slightly branched hydrocarbons having aboiling range above about 40 C. and less than about 200 C., underaromatic conversion conditions with a catalyst comprising the zeolite ofthis invention made substantially free of acidity by neutralizing saidzeolite with a basic metal. Also provided in this invention is such aprocess wherein the zeolite contains a Group VIII metal component.

Also provided by the present invention is a catalytic cracking processcomprising contacting a hydrocarbon feedstock in a reaction zone undercatalytic cracking conditions in the absence of added hydrogen with acatalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. Also included in this invention issuch a catalytic cracking process wherein the catalyst additionallycomprises a large pore crystalline cracking component.

This invention further provides an isomerization process for isomerizingC₄ to C₇ hydrocarbons, comprising contacting a feed having normal andslightly branched C₄ to C₇ hydrocarbons under isomerizing conditionswith a catalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. The zeolite may be impregnated withat least one Group VIII metal, preferably platinum. The catalyst may becalcined in a steam/air mixture at an elevated temperature afterimpregnation of the Group VIII metal.

Also provided by the present invention is a process for alkylating anaromatic hydrocarbon which comprises contacting under alkylationconditions at least a molar excess of an aromatic hydrocarbon with a C₂to C₂₀ olefin under at least partial liquid phase conditions and in thepresence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The olefin may be a C₂ toC₄ olefin, and the aromatic hydrocarbon and olefin may be present in amolar ratio of about 4:1 to about 20:1, respectively. The aromatichydrocarbon may be selected from the group consisting of benzene,toluene, ethylbenzene, xylene, or mixtures thereof.

Further provided in accordance with this invention is a process fortransalkylating an aromatic hydrocarbon which comprises contacting undertransalkylating conditions an aromatic hydrocarbon with a polyalkylaromatic hydrocarbon under at least partial liquid phase conditions andin the presence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The aromatic hydrocarbonand the polyalkyl aromatic hydrocarbon may be present in a molar ratioof from about 1:1 to about 25:1, respectively.

The aromatic hydrocarbon may be selected from the group consisting ofbenzene, toluene, ethylbenzene, xylene, or mixtures thereof, and thepolyalkyl aromatic hydrocarbon may be a dialkylbenzene.

Further provided by this invention is a process to convert paraffins toaromatics which comprises contacting paraffins under conditions whichcause paraffins to convert to aromatics with a catalyst comprising thezeolite of this invention, said catalyst comprising gallium, zinc, or acompound of gallium or zinc.

In accordance with this invention, there is also provided a process forisomerizing olefins comprising contacting said olefin under conditionswhich cause isomerization of the olefin with a catalyst comprising thezeolite of this invention.

Further provided in accordance with this invention is a process forisomerizing an isomerization feed comprising an aromatic C₈ stream ofxylene isomers or mixtures of xylene isomers and ethylbenzene, wherein amore nearly equilibrium ratio of ortho-, meta- and para-xylenes isobtained, said process comprising contacting said feed underisomerization conditions with a catalyst comprising the zeolite of thisinvention.

The present invention further provides a process for oligomerizingolefins comprising contacting an olefin feed under oligomerizationconditions with a catalyst comprising the zeolite of this invention.

This invention also provides a process for converting lower alcohols andother oxygenated hydrocarbons comprising contacting said lower alcoholor other oxygenated hydrocarbon with a catalyst comprising the zeoliteof this invention under conditions to produce liquid products. Thisinvention also provides a process for converting synthesis gas to mainlyliquid hydrocarbons by compositing the zeolite of this invention with aFischer-Tropsch catalyst in an intimate mixture and operating thecomposite under conditions which would normally yield mainly wax withthe FT component alone, as with high-alpha cobalt catalysts at 200C.-250 C., or mainly light olefins with the FT component alone, as withlow-alpha iron catalysts at 250 C.-300 C.

This invention also provides a process for converting synthesis gas tomainly liquid hydrocarbons by compositing the zeolite of this inventionwith a methanol synthesis catalyst in an intimate mixture and operatingthe composite under conditions where the methanol catalyst alone wouldproduce mainly methanol with low yields per pass due to equilibriumconstraints.

Also provided by the present invention is an improved process for thereduction of oxides of nitrogen contained in a gas stream in thepresence of oxygen wherein said process comprises contacting the gasstream with a zeolite, the improvement comprising using as the zeolite azeolite having a mole ratio greater than about 20 of an oxide of a firsttetravalent element to an oxide of a second tetravalent elementdifferent from said first tetravalent element, trivalent element,pentavalent element or mixture thereof and having, after calcination,the X-ray diffraction lines of Table II. The zeolite may contain a metalor metal ions (such as cobalt, copper or mixtures thereof capable ofcatalyzing the reduction of the oxides of nitrogen, and may be conductedin the presence of a stoichiometric excess of oxygen. In a preferredembodiment, the gas stream is the exhaust stream of an internalcombustion engine.

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a family of crystalline, large porezeolites designated herein “zeolite SSZ-53” or simply “SSZ-53”. As usedherein, the term “large pore” means having an average pore size diametergreater than about 6.0 Angstroms, preferably from about 6.5 Angstroms toabout 7.5 Angstroms.

In preparing SSZ-53 zeolites, a phenylcycloalkylmethyl ammonium cationis used as a crystallization template. In general, SSZ-53 is prepared bycontacting an active source of one or more oxides selected from thegroup consisting of monovalent element oxides, divalent element oxides,trivalent element oxides, and tetravalent element oxides with thephenylcycloalkylmethyl ammonium cations templating agents.

SSZ-53 is prepared from a reaction mixture having the composition shownin Table A below.

TABLE A Reaction Mixture Typical Preferred YO₂/W_(a)O_(b) 20-150 35-60OH-/YO₂ 0.1-0.50 0.2-0.3 Q/YO₂ 0.05-0.5 0.1-0.2 M_(2/n)/YO₂ 0.02-0.40.1-0.25 H₂O/YO₂ 25-80 30-45

where Y, W, Q, M and n are as defined above, and a is 1 or 2, and b is 2when a is 1 (i.e., W is tetravalent) and b is 3 when a is 2 (i.e., W istrivalent).

In practice, SSZ-53 is prepared by a process comprising:

(a) preparing an aqueous solution containing sources of at least oneoxide capable of forming a crystalline molecular sieve and aphenylcycloalkylmethyl ammonium cation having an anionic counterionwhich is not detrimental to the formation of SSZ-53;

(b) maintaining the aqueous solution under conditions sufficient to formcrystals of SSZ-53; and

(c) recovering the crystals of SSZ-53.

Accordingly, SSZ-53 may comprise the crystalline material and thetemplating agent in combination with metallic and non-metallic oxidesbonded in tetrahedral coordination through shared oxygen atoms to form across-linked three dimensional crystal structure. The metallic andnon-metallic oxides comprise one or a combination of oxides of a firsttetravalent element(s), and one or a combination of a second tetravalentelement(s) different from the first tetravalent element(s), trivalentelement(s), pentavalent element(s) or mixture thereof. The firsttetravalent element(s) is preferably selected from the group consistingof silicon, germanium and combinations thereof. More preferably, thefirst tetravalent element is silicon. The second tetravalent element(which is different from the first tetravalent element), trivalentelement and pentavalent element is preferably selected from the groupconsisting of aluminum, gallium, iron, boron, titanium, indium, vanadiumand combinations thereof. More preferably, the second trivalent ortetravalent element is aluminum or boron.

Typical sources of aluminum oxide for the reaction mixture includealuminates, alumina, aluminum colloids, aluminum oxide coated on silicasol, hydrated alumina gels such as Al(OH)₃ and aluminum compounds suchas AlCl₃ and Al₂(SO₄)₃. Typical sources of silicon oxide includesilicates, silica hydrogel, silicic acid, fumed silica, colloidalsilica, tetra-alkyl orthosilicates, and silica hydroxides. Boron, aswell as gallium, germanium, titanium, indium, vanadium and iron, can beadded in forms corresponding to their aluminum and silicon counterparts.

A source zeolite reagent may provide a source of aluminum or boron. Inmost cases, the source zeolite also provides a source of silica. Thesource zeolite in its dealuminated or deboronated form may also be usedas a source of silica, with additional silicon added using, for example,the conventional sources listed above. Use of a source zeolite reagentas a source of alumina for the present process is more completelydescribed in U.S. Pat. No. 5,225,179, issued Jul. 6, 1993 to Nakagawaentitled “Method of Making Molecular Sieves”, the disclosure of which isincorporated herein by reference.

Typically, an alkali metal hydroxide and/or an alkaline earth metalhydroxide, such as the hydroxide of sodium, potassium, lithium, cesium,rubidium, calcium, and magnesium, is used in the reaction mixture;however, this component can be omitted so long as the equivalentbasicity is maintained. The templating agent may be used to providehydroxide ion. Thus, it may be beneficial to ion exchange, for example,the halide for hydroxide ion, thereby reducing or eliminating the alkalimetal hydroxide quantity required. The alkali metal cation or alkalineearth cation may be part of the as-synthesized crystalline oxidematerial, in order to balance valence electron charges therein.

The reaction mixture is maintained at an elevated temperature until thecrystals of the SSZ-53 zeolite are formed. The hydrothermalcrystallization is usually conducted under autogenous pressure, at atemperature between 100 C. and 200 C., preferably between 135 C. and 160C. The crystallization period is typically greater than 1 day andpreferably from about 3 days to about 20 days.

Preferably, the zeolite is prepared using mild stirring or agitation.

During the hydrothermal crystallization step, the SSZ-53 crystals can beallowed to nucleate spontaneously from the reaction mixture. The use ofSSZ-53 crystals as seed material can be advantageous in decreasing thetime necessary for complete crystallization to occur. In addition,seeding can lead to an increased purity of the product obtained bypromoting the nucleation and/or formation of SSZ-53 over any undesiredphases. When used as seeds, SSZ-53 crystals are added in an amountbetween 0.1 and 10% of the weight of silica used in the reactionmixture.

Once the zeolite crystals have formed, the solid product is separatedfrom the reaction mixture by standard mechanical separation techniquessuch as filtration. The crystals are water-washed and then dried, e.g.,at 90 C. to 150 C. for from 8 to 24 hours, to obtain the as-synthesizedSSZ-53 zeolite crystals. The drying step can be performed at atmosphericpressure or under vacuum.

SSZ-53, as prepared, has a mole ratio of an oxide selected from siliconoxide, germanium oxide and mixtures thereof to an oxide selected fromaluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide,indium oxide, vanadium oxide and mixtures thereof greater than about 20;and has the X-ray diffraction lines of Table I below. SSZ-53 further hasa composition, as-synthesized and in the anhydrous state, in terms ofmole ratios, shown in Table B below.

TABLE B As-Synthesized SSZ-53 YO₂/W_(c)O_(d) 20-150 M_(2/n)/YO₂0.01-0.03 Q/YO₂ 0.02-0.05

where Y, W, c, d, M and Q are as defined above.

SSZ-53 can be made essentially aluminum free, i.e., having a silica toalumina mole ratio of ∞. A method of increasing the mole ratio of silicato alumina is by using standard acid leaching or chelating treatments.However, essentially aluminum-free SSZ-53 can be synthesized directlyusing essentially aluminum-free silicon sources as the main tetrahedralmetal oxide component, if boron is also present. SSZ-53 can also beprepared directly as either an aluminosilicate or a borosilicate.

Lower silica to alumina ratios may also be obtained by using methodswhich insert aluminum into the crystalline framework. For example,aluminum insertion may occur by thermal treatment of the zeolite incombination with an alumina binder or dissolved source of alumina. Suchprocedures are described in U.S. Pat. No. 4,559,315, issued on Dec. 17,1985 to Chang et al.

It is believed that SSZ-53 is comprised of a new framework structure ortopology which is characterized by its X-ray diffraction pattern. SSZ-53zeolites, as-synthesized, have a crystalline structure whose X-raypowder diffraction pattern exhibit the characteristic lines shown inTable I and is thereby distinguished from other known zeolites.

TABLE I As-Synthesized SSZ-53 2 Theta^((a)) d Relative Intensity^((b))6.65 13.3 VS 8.3 10.6 S 17.75 4.99 S 19.8 4.48 S 21.2 4.19 VS 23.05 3.85W 25.3 3.52 M 35.8 2.51 M ^((a))±0.15 ^((b))The X-ray patterns providedare based on a relative intensity scale in which the strongest line inthe X-ray pattern is assigned a value of 100: W(weak) is less than 20;M(medium) is between 20 and 40; S(strong) is between 40 and 60; VS(verystrong) is greater than 60.

After calcination, the SSZ-53 zeolites have a crystalline structurewhose X-ray powder diffraction pattern include the characteristic linesshown in Table II:

TABLE II Calcined SSZ-53 2 Theta^((a)) d Relative Intensity 6.65 13.3 VS8.3 10.6 S 17.75 4.99 M 19.7 4.50 M 21.0 4.23 M 23.0 3.86 W 25.15 3.544W 35.6 2.52 W ^((a))±0.15

In addition to the peaks in Tables I and II, there are peaks at 2 theta22.0 and 21.6. These peaks may be partially overlapped with the peak at2 theta 21.0, or appear as shoulders. Thus, the peaks at 2 theta 22.0and 21.6 may be difficult to locate, especially if the SSZ-53 has asmall crystal size.

The X-ray powder diffraction patterns were determined by standardtechniques. The radiation was the K-alpha/doublet of copper. The peakheights and the positions, as a function of 2 Theta where Theta is theBragg angle, were read from the relative intensities of the peaks, andd, the interplanar spacing in Angstroms corresponding to the recordedlines, can be calculated.

The variation in the scattering angle (two theta) measurements, due toinstrument error and to differences between individual samples, isestimated at ±0.20 degrees.

The X-ray diffraction pattern of Table I is representative of“as-synthesized” or “as-made” SSZ-53 zeolites. Minor variations in thediffraction pattern can result from variations in the silica-to-aluminaor silica-to-boron mole ratio of the particular sample due to changes inlattice constants. In addition, sufficiently small crystals will affectthe shape and intensity of peaks, leading to significant peakbroadening.

Representative peaks from the X-ray diffraction pattern of calcinedSSZ-53 are shown in Table II. Calcination can also result in changes inthe intensities of the peaks as compared to patterns of the “as-made”material, as well as minor shifts in the diffraction pattern. Thezeolite produced by exchanging the metal or other cations present in thezeolite with various other cations (such as H⁺ or NH₄ ⁺) yieldsessentially the same diffraction pattern, although again, there may beminor shifts in the interplanar spacing and variations in the relativeintensities of the peaks. Notwithstanding these minor perturbations, thebasic crystal lattice remains unchanged by these treatments.

Crystalline SSZ-53 can be used as-synthesized, but preferably will bethermally treated (calcined). Usually, it is desirable to remove thealkali metal cation by ion exchange and replace it with hydrogen,ammonium, or any desired metal ion. The zeolite can be leached withchelating agents, e.g., EDTA or dilute acid solutions, to increase thesilica to alumina mole ratio. The zeolite can also be steamed; steaminghelps stabilize the crystalline lattice to attack from acids.

The zeolite can be used in intimate combination with hydrogenatingcomponents, such as tungsten, vanadium molybdenum, rhenium, nickelcobalt, chromium, manganese, or a noble metal, such as palladium orplatinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

Metals may also be introduced into the zeolite by replacing some of thecations in the zeolite with metal cations via standard ion exchangetechniques (see, for example, U.S. Pat. No. 3,140,249 issued Jul. 7,1964 to Plank et al.; U.S. Pat. No. 3,140,251 issued Jul. 7, 1964 toPlank et al.; and U.S. Pat. No. 3,140,253 issued Jul. 7, 1964 to Planket al.). Typical replacing cations can include metal cations, e.g., rareearth, Group IA, Group IIA and Group VIII metals, as well as theirmixtures. Of the replacing metallic cations, cations of metals such asrare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe areparticularly preferred.

The hydrogen, ammonium, and metal components can be ion-exchanged intothe SSZ-53. The zeolite can also be impregnated with the metals, or themetals can be physically and intimately admixed with the zeolite usingstandard methods known to the art.

Typical ion-exchange techniques involve contacting the synthetic zeolitewith a solution containing a salt of the desired replacing cation orcations. Although a wide variety of salts can be employed, chlorides andother halides, acetates, nitrates, and sulfates are particularlypreferred. The zeolite is usually calcined prior to the ion-exchangeprocedure to remove the organic matter present in the channels and onthe surface, since this results in a more effective ion exchange.Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. No. 3,140,249 issued on Jul. 7, 1964 toPlank et al.; U.S. Pat. No. 3,140,251 issued on Jul. 7, 1964 to Plank etal.; and U.S. Pat. No. 3,140,253 issued on Jul. 7, 1964 to Plank et al.

Following contact with the salt solution of the desired replacingcation, the zeolite is typically washed with water and dried attemperatures ranging from 65 C. to about 200 C. After washing, thezeolite can be calcined in air or inert gas at temperatures ranging fromabout 200 C. to about 800 C. for periods of time ranging from 1 to 48hours, or more, to produce a catalytically active product especiallyuseful in hydrocarbon conversion processes.

Regardless of the cations present in the synthesized form of SSZ-53, thespatial arrangement of the atoms which form the basic crystal lattice ofthe zeolite remains essentially unchanged.

SSZ-53 can be formed into a wide variety of physical shapes. Generallyspeaking, the zeolite can be in the form of a powder, a granule, or amolded product, such as extrudate having a particle size sufficient topass through a 2-mesh (Tyler) screen and be retained on a 400-mesh(Tyler) screen. In cases where the catalyst is molded, such as byextrusion with an organic binder, the aluminosilicate can be extrudedbefore drying, or dried or partially dried and then extruded.

SSZ-53 can be composited with other materials resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Pat.No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which areincorporated by reference herein in their entirety.

Hydrocarbon Conversion Processes

SSZ-53 zeolites are useful in hydrocarbon conversion reactions.Hydrocarbon conversion reactions are chemical and catalytic processes inwhich carbon containing compounds are changed to different carboncontaining compounds. Examples of hydrocarbon conversion reactions inwhich SSZ-53 are expected to be useful include hydrocracking, dewaxing,catalytic cracking and olefin and aromatics formation reactions. Thecatalysts are also expected to be useful in other petroleum refining andhydrocarbon conversion reactions such as isomerizing n-paraffins andnaphthenes, polymerizing and oligomerizing olefinic or acetyleniccompounds such as isobutylene and butene-1, reforming, isomerizingpolyalkyl substituted aromatics (e.g., m-xylene), and disproportionatingaromatics (e.g., toluene) to provide mixtures of benzene, xylenes andhigher methylbenzenes and oxidation reactions. Also included arerearrangement reactions to make various naphthalene derivatives. TheSSZ-53 catalysts may have high selectivity, and under hydrocarbonconversion conditions can provide a high percentage of desired productsrelative to total products.

SSZ-53 zeolites can be used in processing hydrocarbonaceous feedstocks.Hydrocarbonaceous feedstocks contain carbon compounds and can be frommany different sources, such as virgin petroleum fractions, recyclepetroleum fractions, shale oil, liquefied coal, tar sand oil, syntheticparaffins from NAO, recycled plastic feedstocks and, in general, can beany carbon containing feedstock susceptible to zeolitic catalyticreactions. Depending on the type of processing the hydrocarbonaceousfeed is to undergo, the feed can contain metal or be free of metals; itcan also have high or low nitrogen or sulfur impurities. It can beappreciated, however, that in general processing will be more efficient(and the catalyst more active) the lower the metal, nitrogen, and sulfurcontent of the feedstock.

The conversion of hydrocarbonaceous feeds can take place in anyconvenient mode, for example, in fluidized bed, moving bed, or fixed bedreactors depending on the types of process desired. The formulation ofthe catalyst particles will vary depending on the conversion process andmethod of operation.

Other reactions which can be performed using the catalyst of thisinvention containing a metal, e.g., a Group VIII metal such platinum,include hydrogenation-dehydrogenation reactions, denitrogenation anddesulfurization reactions.

The following Table III indicates typical reaction conditions which maybe employed when using catalysts comprising SSZ-53 in the hydrocarbonconversion reactions of this invention. Preferred conditions areindicated in parentheses.

TABLE III Temp., Process C. Pressure LHSV Hydrocracking 175-485 0.5-350bar 0.1-30 Dewaxing 200-475 15-3000 psig 0.1-20 (250-450) (200-3000)(0.2-10) Aromatics formation 400-600 atm.-10 bar 0.1-15 (480-550) Cat.cracking 127-885 subatm.-¹ 0.5-50 (atm.-5 atm.) Oligomerization 232-649²0.1-50 atm.^(2,3) 0.2-50² 10-232⁴ — 0.05-20⁵ (27-204)⁴ — (0.1-10)⁵Paraffins to aromatics 100-700 0-1000 psig 0.5-40⁵ Condensation of260-538 0.5-1000 psig 0.5-50⁵ alcohols Isomerization 93-538 50-1000 psig1-10 (204-315) (1-4) Xylene isomerization 260-593² 0.5-50 atm.² 0.1-100⁵(315-566)² (1-5 atm)² (0.5-50)⁵ 38-371⁴ 1-200 atm.⁴ 0.5-50 Liquid PhaseAlkylation 37-315 50-1000 psig 0.5 to 50⁵ of Aromatics by Small Olefins¹Several hundred atmospheres ²Gas phase reaction ³Hydrocarbon partialpressure ⁴Liquid phase reaction ⁵WHSV

Other reaction conditions and parameters are provided below.

Hydrocracking

Using a catalyst which comprises SSZ-53, preferably predominantly in thehydrogen form, and a hydrogenation promoter, heavy petroleum residualfeedstocks, cyclic stocks and other hydrocrackate charge stocks can behydrocracked using the process conditions and catalyst componentsdisclosed in the aforementioned U.S. Pat. Nos. 4,910,006 and 5,316,753.

The hydrocracking catalysts contain an effective amount of at least onehydrogenation component of the type commonly employed in hydrocrackingcatalysts. The hydrogenation component is generally selected from thegroup of hydrogenation catalysts consisting of one or more metals ofGroup VIB and Group VIII, including the salts, complexes and solutionscontaining such. The hydrogenation catalyst is preferably selected fromthe group of metals, salts and complexes thereof of the group consistingof at least one of platinum, palladium, rhodium, iridium, ruthenium andmixtures thereof or the group consisting of at least one of nickel,molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof.Reference to the catalytically active metal or metals is intended toencompass such metal or metals in the elemental state or in some formsuch as an oxide, sulfide, halide, carboxylate and the like. Thehydrogenation catalyst is present in an effective amount to provide thehydrogenation function of the hydrocracking catalyst, and preferably inthe range of from 0.05 to 25% by weight.

Dewaxing

SSZ-53, preferably predominantly in the hydrogen form, can be used todewax hydrocarbonaceous feeds by selectively removing straight chainparaffins. Typically, the viscosity index of the dewaxed product isimproved (compared to the waxy feed) when the waxy feed is contactedwith SSZ-53 under isomerization dewaxing conditions. The catalyticdewaxing conditions are dependent in large measure on the feed used andupon the desired pour point. Hydrogen is preferably present in thereaction zone during the catalytic dewaxing process. The hydrogen tofeed ratio is typically between about 500 and about 30,000 SCF/bbl(standard cubic feet per barrel), preferably about 1000 to about 20,000SCF/bbl. Generally, hydrogen will be separated from the product andrecycled to the reaction zone. Typical feedstocks include light gas oil,heavy gas oils and reduced crudes boiling above about 350 F.

A typical dewaxing process is the catalytic dewaxing of a hydrocarbonoil feedstock boiling above about 350 F. and containing straight chainand slightly branched chain hydrocarbons by contacting the hydrocarbonoil feedstock in the presence of added hydrogen gas at a hydrogenpressure of about 15-3000 psi with a catalyst comprising SSZ-53 and atleast one Group VIII metal.

The SSZ-53 hydrodewaxing catalyst may optionally contain a hydrogenationcomponent of the type commonly employed in dewaxing catalysts. See theaforementioned U.S. Pat. Nos. 4,910,006 and 5,316,753 for examples ofthese hydrogenation components.

The hydrogenation component is present in an effective amount to providean effective hydrodewaxing and hydroisomerization catalyst preferably inthe range of from about 0.05 to 5% by weight. The catalyst may be run insuch a mode to increase isodewaxing at the expense of crackingreactions.

The feed may be hydrocracked, followed by dewaxing. This type oftwo-stage process and typical hydrocracking conditions are described inU.S. Pat. No. 4,921,594, issued May 1, 1990 to Miller, which isincorporated herein by reference in its entirety.

SSZ-53 may also be utilized as a dewaxing catalyst in the form of alayered catalyst. That is, the catalyst comprises a first layercomprising zeolite SSZ-53 and at least one Group VIII metal, and asecond layer comprising an aluminosilicate zeolite which is more shapeselective than zeolite SSZ-53. The use of layered catalysts is disclosedin U.S. Pat. No. 5,149,421, issued Sep. 22, 1992 to Miller, which isincorporated by reference herein in its entirety. The layering may alsoinclude a bed of SSZ-53 layered with a non-zeolitic component designedfor either hydrocracking or hydrofinishing.

SSZ-53 may also be used to dewax raffinates, including bright stock,under conditions such as those disclosed in U.S. Pat. No. 4,181,598,issued Jan. 1, 1980 to Gillespie et al., which is incorporated byreference herein in its entirety.

It is often desirable to use mild hydrogenation (sometimes referred toas hydrofinishing) to produce more stable dewaxed products. Thehydrofinishing step can be performed either before or after the dewaxingstep, and preferably after. Hydrofinishing is typically conducted attemperatures ranging from about 190 C. to about 340 C. at pressures fromabout 400 psig to about 3000 psig at space velocities (LHSV) betweenabout 0.1 and 20 and a hydrogen recycle rate of about 400 to 1500SCF/bbl. The hydrogenation catalyst employed must be active enough notonly to hydrogenate the olefins, diolefins and color bodies which may bepresent, but also to reduce the aromatic content. Suitable hydrogenationcatalyst are disclosed in U.S. Pat. No. 4,921,594, issued May 1, 1990 toMiller, which is incorporated by reference herein in its entirety. Thehydrofinishing step is beneficial in preparing an acceptably stableproduct (e.g., a lubricating oil) since dewaxed products prepared fromhydrocracked stocks tend to be unstable to air and light and tend toform sludges spontaneously and quickly.

Lube oil may be prepared using SSZ-53. For example, a C₂₀+ lube oil maybe made by isomerizing a C₂₀+ olefin feed over a catalyst comprisingSSZ-53 in the hydrogen form and at least one Group VIII metal.Alternatively, the lubricating oil may be made by hydrocracking in ahydrocracking zone a hydrocarbonaceous feedstock to obtain an effluentcomprising a hydrocracked oil, and catalytically dewaxing the effluentat a temperature of at least about 400 F. and at a pressure of fromabout 15 psig to about 3000 psig in the presence of added hydrogen gaswith a catalyst comprising SSZ-53 in the hydrogen form and at least oneGroup VIII metal.

Aromatics Formation

SSZ-53 can be used to convert light straight run naphthas and similarmixtures to highly aromatic mixtures. Thus, normal and slightly branchedchained hydrocarbons, preferably having a boiling range above about 40C. and less than about 200 C., can be converted to products having asubstantial higher octane aromatics content by contacting thehydrocarbon feed with a catalyst comprising SSZ-53. It is also possibleto convert heavier feeds into BTX or naphthalene derivatives of valueusing a catalyst comprising SSZ-53.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium or tin or amixture thereof may also be used in conjunction with the Group VIIImetal compound and preferably a noble metal compound. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inreforming catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

It is critical to the selective production of aromatics in usefulquantities that the conversion catalyst be substantially free ofacidity, for example, by neutralizing the zeolite with a basic metal,e.g., alkali metal, compound. Methods for rendering the catalyst free ofacidity are known in the art. See the aforementioned U.S. Pat. Nos.4,910,006 and 5,316,753 for a description of such methods.

The preferred alkali metals are sodium, potassium, rubidium and cesium.The zeolite itself can be substantially free of acidity only at veryhigh silica:alumina mole ratios.

Catalytic Cracking

Hydrocarbon cracking stocks can be catalytically cracked in the absenceof hydrogen using SSZ-53, preferably predominantly in the hydrogen form.

When SSZ-53 is used as a catalytic cracking catalyst in the absence ofhydrogen, the catalyst may be employed in conjunction with traditionalcracking catalysts, e.g., any aluminosilicate heretofore employed as acomponent in cracking catalysts. Typically, these are large pore,crystalline aluminosilicates. Examples of these traditional crackingcatalysts are disclosed in the aforementioned U.S. Pat. Nos. 4,910,006and 5,316,753. When a traditional cracking catalyst (TC) component isemployed, the relative weight ratio of the TC to the SSZ-53 is generallybetween about 1:10 and about 500:1, desirably between about 1:10 andabout 200:1, preferably between about 1:2 and about 50:1, and mostpreferably is between about 1:1 and about 20:1. The novel zeolite and/orthe traditional cracking component may be further ion exchanged withrare earth ions to modify selectivity.

The cracking catalysts are typically employed with an inorganic oxidematrix component. See the aforementioned U.S. Pat. Nos. 4,910,006 and5,316,753 for examples of such matrix components.

Isomerization

The present catalyst is highly active and highly selective forisomerizing C₄ to C₇ hydrocarbons. The activity means that the catalystcan operate at relatively low temperature which thermodynamically favorshighly branched paraffins. Consequently, the catalyst can produce a highoctane product. The high selectivity means that a relatively high liquidyield can be achieved when the catalyst is run at a high octane.

The present process comprises contacting the isomerization catalyst,i.e., a catalyst comprising SSZ-53 in the hydrogen form, with ahydrocarbon feed under isomerization conditions. The feed is preferablya light straight run fraction, boiling within the range of 30 F. to 250F. and preferably from 60 F. to 200 F. Preferably, the hydrocarbon feedfor the process comprises a substantial amount of C₄ to C₇ normal andslightly branched low octane hydrocarbons, more preferably C₅ and C₆hydrocarbons. It is preferable to carry out the isomerization reactionin the presence of hydrogen. Preferably, hydrogen is added to give ahydrogen to hydrocarbon ratio (H₂/HC) of between 0.5 and 10 H₂/HC, morepreferably between 1 and 8 H₂/HC. See the aforementioned U.S. Pat. Nos.4,910,006 and 5,316,753 for a further discussion of isomerizationprocess conditions.

A low sulfur feed is especially preferred in the present process. Thefeed preferably contains less than 10 ppm, more preferably less than 1ppm, and most preferably less than 0.1 ppm sulfur. In the case of a feedwhich is not already low in sulfur, acceptable levels can be reached byhydrogenating the feed in a presaturation zone with a hydrogenatingcatalyst which is resistant to sulfur poisoning. See the aforementionedU.S. Pat. Nos. 4,910,006 and 5,316,753 for a further discussion of thishydrodesulfurization process.

It is preferable to limit the nitrogen level and the water content ofthe feed. Catalysts and processes which are suitable for these purposesare known to those skilled in the art.

After a period of operation, the catalyst can become deactivated bysulfur or coke. See the aforementioned U.S. Pat. Nos. 4,910,006 and5,316,753 for a further discussion of methods of removing this sulfurand coke, and of regenerating the catalyst.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium and tin mayalso be used in conjunction with the noble metal. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inisomerizing catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

Alkylation and Transalkylation

SSZ-53 can be used in a process for the alkylation or transalkylation ofan aromatic hydrocarbon. The process comprises contacting the aromatichydrocarbon with a C₂ to C₁₆ olefin alkylating agent or a polyalkylaromatic hydrocarbon transalkylating agent, under at least partialliquid phase conditions, and in the presence of a catalyst comprisingSSZ-53.

SSZ-53 can also be used for removing benzene from gasoline by alkylatingthe benzene as described above and removing the alkylated product fromthe gasoline.

For high catalytic activity, the SSZ-53 zeolite should be predominantlyin its hydrogen ion form. It is preferred that, after calcination, atleast 80% of the cation sites are occupied by hydrogen ions and/or rareearth ions.

Examples of suitable aromatic hydrocarbon feedstocks which may bealkylated or transalkylated by the process of the invention includearomatic compounds such as benzene, toluene and xylene. The preferredaromatic hydrocarbon is benzene. There may be occasions wherenaphthalene derivatives such as dimethylnaphthalene may be desirable.Mixtures of aromatic hydrocarbons may also be employed.

Suitable olefins for the alkylation of the aromatic hydrocarbon arethose containing 2 to 20 carbon atoms, preferably 2 to 4 carbon atoms,such as ethylene, propylene, butene-1, trans-butene-2 and cis-butene-2,or mixtures thereof. There may be instances where pentenes aredesirable. The preferred olefins are ethylene and propylene. Longerchain alpha olefins may be used as well.

When transalkylation is desired, the transalkylating agent is apolyalkyl aromatic hydrocarbon containing two or more alkyl groups thateach may have from 2 to about 4 carbon atoms. For example, suitablepolyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkylaromatic hydrocarbons, such as diethylbenzene, triethylbenzene,diethylmethylbenzene (diethyltoluene), di-isopropylbenzene,di-isopropyltoluene, dibutylbenzene, and the like. Preferred polyalkylaromatic hydrocarbons are the dialkyl benzenes. A particularly preferredpolyalkyl aromatic hydrocarbon is di-isopropylbenzene.

When alkylation is the process conducted, reaction conditions are asfollows. The aromatic hydrocarbon feed should be present instoichiometric excess. It is preferred that molar ratio of aromatics toolefins be greater than four-to-one to prevent rapid catalyst fouling.The reaction temperature may range from 100 F. to 600 F. preferably 250F. to 450 F. The reaction pressure should be sufficient to maintain atleast a partial liquid phase in order to retard catalyst fouling. Thisis typically 50 psig to 1000 psig depending on the feedstock andreaction temperature. Contact time may range from 10 seconds to 10hours, but is usually from 5 minutes to an hour. The weight hourly spacevelocity (WHSV), in terms of grams (pounds) of aromatic hydrocarbon andolefin per gram (pound) of catalyst per hour, is generally within therange of about 0.5 to 50.

When transalkylation is the process conducted, the molar ratio ofaromatic hydrocarbon will generally range from about 1:1 to 25:1, andpreferably from about 2:1 to 20:1. The reaction temperature may rangefrom about 100 F. to 600 F. but it is preferably about 250 F. to 450 F.The reaction pressure should be sufficient to maintain at least apartial liquid phase, typically in the range of about 50 psig to 1000psig, preferably 300 psig to 600 psig. The weight hourly space velocitywill range from about 0.1 to 10. U.S. Pat. No. 5,082,990 issued on Jan.21, 1992 to Hsieh et al. describes such processes and is incorporatedherein by reference.

Conversion of Paraffins to Aromatics

SSZ-53 can be used to convert light gas C₂-C₆ paraffins to highermolecular weight hydrocarbons including aromatic compounds. Preferably,the zeolite will contain a catalyst metal or metal oxide wherein saidmetal is selected from the group consisting of Groups IB, IIB, VIII andIIIA of the Periodic Table. Preferably, the metal is gallium, niobium,indium or zinc in the range of from about 0.05 to 5% by weight.

Xylene Isomerization

SSZ-53 may also be useful in a process for isomerizing one or morexylene isomers in a C₈ aromatic feed to obtain ortho-, meta-, andpara-xylene in a ratio approaching the equilibrium value. In particular,xylene isomerization is used in conjunction with a separate process tomanufacture para-xylene. For example, a portion of the para-xylene in amixed C₈ aromatics stream may be recovered by crystallization andcentrifugation. The mother liquor from the crystallizer is then reactedunder xylene isomerization conditions to restore ortho-, meta- andpara-xylenes to a near equilibrium ratio. At the same time, part of theethylbenzene in the mother liquor is converted to xylenes or to productswhich are easily separated by filtration. The isomerate is blended withfresh feed and the combined stream is distilled to remove heavy andlight by-products. The resultant C₈ aromatics stream is then sent to thecrystallizer to repeat the cycle.

Optionally, isomerization in the vapor phase is conducted in thepresence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene(e.g., ethylbenzene). If hydrogen is used, the catalyst should compriseabout 0.1 to 2.0 wt. % of a hydrogenation/dehydrogenation componentselected from Group VIII (of the Periodic Table) metal component,especially platinum or nickel. By Group VIII metal component is meantthe metals and their compounds such as oxides and sulfides.

Optionally, the isomerization feed may contain 10 to 90 wt. % of adiluent such as toluene, trimethylbenzene, naphthenes or paraffins.

Oligomerization

It is expected that SSZ-53 can also be used to oligomerize straight andbranched chain olefins having from about 2 to 21 carbon atoms andpreferably 2-5 carbon atoms. The oligomers which are the products of theprocess are medium to heavy olefins which are useful for both fuels,i.e., gasoline or a gasoline blending stock and chemicals.

The oligomerization process comprises contacting the olefin feedstock inthe gaseous or liquid phase with a catalyst comprising SSZ-53.

The zeolite can have the original cations associated therewith replacedby a wide variety of other cations according to techniques well known inthe art. Typical cations would include hydrogen, ammonium and metalcations including mixtures of the same. Of the replacing metalliccations, particular preference is given to cations of metals such asrare earth metals, manganese, calcium, as well as metals of Group II ofthe Periodic Table, e.g., zinc, and Group VIII of the Periodic Table,e.g., nickel. One of the prime requisites is that the zeolite have afairly low aromatization activity, i.e., in which the amount ofaromatics produced is not more than about 20% by weight. This isaccomplished by using a zeolite with controlled acid activity [alphavalue] of from about 0.1 to about 120, preferably from about 0.1 toabout 100, as measured by its ability to crack n-hexane.

Alpha values are defined by a standard test known in the art, e.g., asshown in U.S. Pat. No. 3,960,978 issued on Jun. 1, 1976 to Givens et al.which is incorporated totally herein by reference. If required, suchzeolites may be obtained by steaming, by use in a conversion process orby any other method which may occur to one skilled in this art.

Condensation of Alcohols

SSZ-53 can be used to condense lower aliphatic alcohols having 1 to 10carbon atoms to a gasoline boiling point hydrocarbon product comprisingmixed aliphatic and aromatic hydrocarbon. The process disclosed in U.S.Pat. No. 3,894,107, issued Jul. 8, 1975 to Butter et al., describes theprocess conditions used in this process, which patent is incorporatedtotally herein by reference.

The catalyst may be in the hydrogen form or may be base exchanged orimpregnated to contain ammonium or a metal cation complement, preferablyin the range of from about 0.05 to 5% by weight. The metal cations thatmay be present include any of the metals of the Groups I through VIII ofthe Periodic Table. However, in the case of Group IA metals, the cationcontent should in no case be so large as to effectively inactivate thecatalyst, nor should the exchange be such as to eliminate all acidity.There may be other processes involving treatment of oxygenatedsubstrates where a basic catalyst is desired.

Other Uses for SSZ-53

SSZ-53 can also be used as an adsorbent with high selectivities based onmolecular sieve behavior and also based upon preferential hydrocarbonpacking within the pores.

SSZ-53 may also be used for the catalytic reduction of the oxides ofnitrogen in a gas stream. Typically, the gas stream also containsoxygen, often a stoichiometric excess thereof. Also, the SSZ-53 maycontain a metal or metal ions within or on it which are capable ofcatalyzing the reduction of the nitrogen oxides. Examples of such metalsor metal ions include copper, cobalt and mixtures thereof.

One example of such a process for the catalytic reduction of oxides ofnitrogen in the presence of a zeolite is disclosed in U.S. Pat. No.4,297,328, issued Oct. 27, 1981 to Ritscher et al., which isincorporated by reference herein. There, the catalytic process is thecombustion of carbon monoxide and hydrocarbons and the catalyticreduction of the oxides of nitrogen contained in a gas stream, such asthe exhaust gas from an internal combustion engine. The zeolite used ismetal ion-exchanged, doped or loaded sufficiently so as to provide aneffective amount of catalytic copper metal or copper ions within or onthe zeolite. In addition, the process is conducted in an excess ofoxidant, e.g., oxygen.

EXAMPLES

The following examples demonstrate but do not limit the presentinvention.

Index of Examples

Example 1: Preparation of Template A, B, C, D, and E.

Example 2-5: Preparation of borosilicate SSZ-53 having a >30 SiO₂/B₂O₃ratio with Templates A, B, C, and D.

Example 6: Preparation of Aluminosilicate SSZ-53 having a >30 SiO₂/Al₂O₃ratio with Template E.

Example 7: Seeded Preparation of SSZ-53.

Example 8: Preparation of Borosilicate SSZ-53 at Varying SiO₂/B₂O₃ratios.

Example 9: Calcination of Borosilicate SSZ-53.

Example 10: Making Al-SSZ-53 from B-SSZ-53.

Example 11: Calcination of Al-SSZ-53.

Example 12: NH₄ Exchange of Aluminosilicate SSZ-53.

Example 13: N₂ Micropore Volume.

Example 14: Constraint Index Determination.

Example 15: Hydrocracking of n-Hexadecane.

The templating agents indicated in Table IV below are used in theseexamples.

TABLE IV

N,N,N-trimethyl-[1-(4-fluorophenyl)cyclopentyl]methyl ammonium hydroxide(Template A)

N,N,N-trimethyl-[1-(3-fluorophenyl)cyclopentyl]methyl ammonium hydroxide(Template B)

N,N,N-trimethyl-[1-(2-fluorophenyl)cyclopentyl]methyl ammonium hydroxide(Template C)

N,N,N-trimethyl-1-phenylcyclohexyl methyl ammonium hydroxide (TemplateD)

N,N,N-trimethyl-1-phenylcyclopentyl methyl ammonium hydroxide (TemplateE)

Example 1 shows synthesis of the structure-directing agents.

Example 1

Synthesis of N,N,N-trimethyl-[1-(4-fluorophenyl)cyclopentyl]methylammonium cation (Template A)

The structure directing agents A, B, C, D and E were prepared accordingto the procedure described below for the synthesis ofN,N,N-trimethyl-[1-(4-fluorophenyl)cyclopentyl]methyl ammonium cation(Template A). The synthesis ofN,N,N-trimethyl-[1-(4-fluorophenyl)cyclopentyl]methyl ammonium cation(A) is a representative example. In a 2 Liter volume three-necked roundbottom reaction flask equipped with a mechanical stirrer and refluxcondenser with a drying tube, 15 grams (0.4 mole) of lithium aluminumhydride (95% purity; Aldrich) were suspended in 400 ml anhydroustetrahydrofuran (THF; Aldrich) and stirred at room temperature for 15minutes. The dark gray suspension was cooled down to 0 C. by means of anice-bath. To the suspension 25 gm (0.132 mole) of1-(4-fluoruphenyl)cyclopentylcarbonitrile (ACROS ORGANICS) in 50 mlanhydrous THF were added drop wise via an addition funnel. Once theaddition was completed, the ice bath was replaced with a heating mantle,and the reaction mixture was refluxed over night. The reaction mixturewas cooled down to 0 C. (ice-bath) and diluted with 500-ml ethyl ether.The reaction was worked up by adding 60 ml of 15% w/w aqueous solutionof NaOH drop wise (via an addition funnel) with vigorous stirring. Then,15 ml water was added and the reaction was allowed to stir for anadditional 30 minutes and then allowed to settle. The milky solutionquickly turned into a colorless liquid layer and a fine white powder,which precipitate to the bottom of the flask. The reaction mixture wasfiltered and the solids were thoroughly rinsed with ethyl ether. Theether filtrates were combined and dried over MgSO₄, filtered andconcentrated to give 24.5 grams of colorless oil whose ¹H-NMR and¹³C-NMR data were acceptable for the expected amine;[1-(4-fluorophenyl)cyclopentyl]methyl amine.

Quaternization: The obtained [1-(4-fluorophenyl)cyclopentyl]methylamine. (24 gm; 0.124 mole) was dissolved in 300 ml methanol (ACSreagent). To this solution, 38 gm (0.375 mole) of KHCO₃ and 80 gm (0.56mole) of methyl iodide were added and the resulting mixture was stirredat room temperature for 48 hrs and then was heated at reflux for 6 hrs.The resulting cloudy solution was concentrated under reduced pressure ona rotary evaporator to give a white solid material. The solids wererinsed several times with chloroform and filtered after each rinse. Allthe rinses were combined and concentrated to give a white powder whoseNMR data were agreeable for the desired quaternary ammonium iodide salt.The reaction afforded 40.5 gm (90% yield) of the product.Recrystallization of the powder from isopropyl alcohol gave 38 gm ofpure N,N,N,-trimethyl-[1-(4-fluorophenyl)cyclopentyl]methyl ammoniumiodide salt as shinny white flakes.

Ion Exchange: The obtainedN,N,N-trimethyl-[1-(4-fluorophenyl)cyclopentyl]methyl ammonium iodidesalt (37 gm; 0.1 mol) was dissolved in 120 ml water in a 500-ml volumeplastic bottle. To the solution, 130 gm of Ion-Exchange Resin (BIO RAD®)AG1-X8 ion exchange resin, hydroxide form) were added and the mixturewas stirred at room temperature overnight. The mixture was filtered andthe solids were rinsed with additional 80 ml of water. The originalfiltrate and the rinse were combined and a small aliquot was titratedwith 0.1N HCl to indicate the presence of 95 mmol hydroxide (95 mmoltemplate A) in the solution. The synthetic scheme described above isdepicted in Scheme 1 below.

The synthetic procedure described above was also used to preparetemplates B. C, D and E from the starting nitriles1-(3-fluorophenyl)cyclopentylcarbonitrile,1-(2-fluorophenyl)cyclopentylcarbonitrile,1-phenylcyclohexylcarbonitrile, and 1-phenylcyclopentylcarbonitrile,respectively.

Example 2-5

Preparation of Borosilicate SSZ-53 Starting SiO₂/B₂O₃=46

Table V below summarizes the crystallization experiments and data forthe different templating agents A, B, C, and D used in the synthesis ofSSZ-53. In a typical run, 3 mmol of the templating agent, 1.2 mmol ofNaOH, 0.16 mmol of sodium borate decahydrate (Na₂B₄O₇.10H₂O) and 14.8mmol of SiO₂ (0.9 gm of CABOSIL-M-5) were mixed in 11.25 gm ofde-ionized water (625 mmol) in a 23 cc Teflon liner. The components werethoroughly mixed in the liner and the resulting gel was capped off andplaced in a Parr reactor and heated in an oven at 160 C. while rotatingat 43 rpm. The reaction was monitored by checking the gel's pH, and bylooking for crystal formation using Scanning Electron Microscopy (SEM)every six days. The reaction is usually completed within 12-21 days. Theresulting reaction mixture is then filtered through a fritted-glassfunnel, and the collected solids are washed several times with water (atotal of 1 liter) and allowed to air-dry over night. The solid productis further dried in an oven at 120 C. for 1 hour. The typical yield is80-90% (based on the starting solid mass). The product is then analyzedand characterized by SEM and powder XRD.

TABLE V Example Cation SiO₂/B₂O₃ SiO₂/—OH SiO₂/Na H₂O/SiO₂ Time (days)Product 2 A 46 3.5 9.7 42 18 SSZ-53 3 B 46 3.5 9.7 42 18 SSZ-53 4 C 463.5 9.7 42 21 SSZ-53 5 D 46 3.5 9.6 42 12 SSZ-53

Analysis by XRD shows the product to be SSZ-53. The XRD data appears inTable VI below (the XRD data shown in table VI is for the sample ofExample 2).

TABLE VI Two Theta(deg.) d-spacing (Å) Intensity I/I₀ 5.15 17.15 2 6.6513.28 100 7.75 11.40 2 8.30 10.64 63 9.75 9.064 2 13.55 6.530 12 15.705.640 2 16.25 5.450 8 16.70 5.304 6 17.55 5.049 20 17.75 4.993 33 18.354.831 3 19.30 4.595 6 19.75 4.492 23 21.15 4.197 66 21.60 4.111 12 22.004.037 39 22.45 3.957 6 23.00 3.864 12 23.20 3.831 4 23.45 3.791 9 24.453.638 8 25.25 3.524 30 25.85 3.444 9 26.25 3.392 4 26.60 3.348 7 26.903.312 14 27.40 3.252 20 27.90 3.195 6 29.15 3.061 8 29.75 3.001 6 30.902.892 5 31.30 2.855 4 32.15 2.782 3 32.80 2.728 4 34.10 2.627 2 34.352.609 3 35.15 2.551 2 35.75 2.510 16 36.40 2.466 5 37.35 2.406 4

Example 6

Preparation of Aluminosilicate SSZ-53 Starting SiO₂/Al₂O₃=70 WithTemplate E

To a solution of N,N,N-trimethyl-(1-Phenylcyclopentyl)methyl ammoniumhydroxide (˜3 mmol; 7.5 gm of 0.40 molar Template E solution) and 0.75mmol NaOH (0.75 gm of 1 N aqueous solution) in a 23 cc Teflon cup, a0.25 gm of sodium-Y zeolite (Union Carbide's LZ-210) and 0.75 gm ofCABOSIL-M-5 (SiO₂) were added, consecutively. The mixture was thoroughlystirred and the resulting gel was capped off and placed in a Parrreactor and heated in an oven at 160 C. while rotating at 43 rpm. Thereaction was monitored by checking the gel's pH, and by looking forcrystal formation using Scanning Electron Microscopy (SEM) at six daysintervals. The reaction was completed after heating at the temperaturedescribed above (while rotating at 43 rpm)) for 12 days. The reactionmixture appeared as a paste, which was crystalline by SEM analysis. Thepaste was diluted with de ionized water and filtered through afritted-glass funnel. The resulting solid was washed generously withwater and allowed to air-dry over night to yield 1.0 gm of a fine whitepowder. The material was found to be SSZ-53 by XRD. A trace amount ofunconverted LZ-210 was also present in the powder as indicated by XRD

Example 7

Seeded Preparation of Borosilicate SSZ-53

The reactions described in examples 2-5 (Table II) were repeated, withthe exception of seeding with 0.05 gram of SSZ-53 crystals. In thiscase, SSZ-53 was obtained in 6-8 days.

Example 8

Preparation of Borosilicate SSZ-53 at Varying SiO₂/B₂O₃ Ratios

Three mmol of a solution of Template A (6.67 grams, 0.45 mmol OH⁻/g) ismixed with 1.2 grams of 1.0 N NaOH and 4.15 grams of water. Sodiumborate decahydrate (0.01-0.12 gram) is added to this solution andstirred until all of the solids have dissolved. Cabosil-M-5 fumed silica(0.9 gram) is then added to the solution and the resulting mixture isheated at 160 C. and rotated at 43 rpm for 12-30 days. The products ofeach of the reactions was filtered, washed, dried and determined by XRDanalysis.

The data presented in Table VII below is obtained from attempts aimed atmaking SSZ-53 (borosilicate) at different SiO₂/B₂O₃ ratios while keepingthe ratio of SiO₂ to other reagents constant using Templates A as thestructure-directing agent.

TABLE VII* SiO₂/B₂O₃ XRD results 282 Cristobalite (major), SSZ-53(minor) 141 Cristobalite (major), SSZ-53 (minor) 94 SSZ-53 70.5 SSZ-5356 SSZ-53 47 SSZ-53 40.25 SSZ-53 35.25 SSZ-53 31.3 SSZ-53 28.2 SSZ-5325.5 SSZ-53 23.5 SSZ-53 *SiO₂/OH for all runs was 3.5; SiO₂/Na for allruns was 12.3 and H₂O/SiO₂ for all runs was 42.

The data presented in Table VIII below is obtained from attempts aimedat making SSZ-53 (borosilicate) at different SiO₂/B₂O₃ ratios whilekeeping the ratio of SiO₂ to other reagents constant using Templates Eas the structure-directing agent.

TABLE VIII SiO₂/B₂O₃ XRD results 282 Cristobalite 141 Cristobalite 94Cristobalite, SSZ-53 (trace) 70.5 Cristobalite, SSZ-53 (minor) 56 SSZ-5347 SSZ-53 40.25 SSZ-53 35.25 SSZ-53 31.3 SSZ-53 28.2 SSZ-53 25.5 SSZ-5323.5 SSZ-53 *SiO₂/OH for all runs was 3.5; SiO₂/Na for all runs was 12.3and H₂O/SiO₂ for all runs was 42.

Example 9

Calcination of B-SSZ-53

The material from Examples 2-5 (the product of each example werecalcined separately) is calcined in the following manner. A thin bed ofmaterial is heated in a muffle furnace from room temperature to 120 C.at a rate of 1 C. per minute and held at 120 C. for three hours. Thetemperature is then ramped up to 540 C. at the same rate and held atthis temperature for 5 hours, after which it is increased to 594 C. andheld there for another 5 hours. A nitrogen stream with a slight bleed ofair is passed over the zeolite at a rate of 20 standard cubic feet perminute during heating. The X-ray diffraction data for the calcinedproduct from example 2 is provided in Table IX below.

TABLE IX 2 Theta d I/I₀ × 100 5.15 17.15 5 6.60 13.38 100 8.25 10.71 579.75 9.064 3 15.65 5.658 2 16.25 5.450 2 17.75 4.993 12 18.25 4.857 219.25 4.607 4 19.70 4.503 12 21.00 4.227 18 21.50 4.130 9 21.95 4.046 522.95 3.872 5 24.45 3.638 1 25.15 3.538 6 25.80 3.450 1 26.30 3.386 126.90 3.312 3 27.25 3.270 3 27.65 3.224 2 29.15 3.061 2 29.65 3.011 230.90 2.892 2 32.85 2.724 1 34.20 2.620 1 35.15 2.551 1 35.60 2.520 436.30 2.473 1

Example 10

Making Al-SSZ-53 from B-SSZ-53

The Boron-SSZ-53 (the product of each of the examples 2-5 were treatedindividually and were not combined) was treated with aluminum nitrate(Al(NO₃)₃.9H₂O) to exchange the boron in the framework of the zeolitewith aluminum to make the more acidic version Al-SSZ-53. The product ofExamples 2-5, after being calcined as in Example 9, was heated in anoven at 95 C. in a 1.0 molar solution of Al(NO₃)₃.9 H₂O (25 ml/1 g ofzeolite) overnight. The mixture was then filtered, treated with diluteHCl and thoroughly rinsed with water. The collected solid was thenrinsed with 0.1 N HCl to remove any excess of aluminum nitrate andwashed again with water. The solids were air-dried overnight andcalcined at 540 C. for 5 hrs to give the H⁺ form of the more acidicversion of SSZ-53.

Example 11

Calcination of Al-SSZ-53

The procedure described in Example 10 is followed on the product fromExample 4, with the exception that the calcination was performed in a50/50 mixture of air and nitrogen stream.

Example 12

NH₄ Exchange

Ion exchange of calcined SSZ-53 material (prepared in Example 9) wasperformed using NH₄NO₃ to convert the zeolite from its Na⁺ form to theNH₄ ⁺ form, and, ultimately, the H⁺ form. Typically, the same mass ofNH₄NO₃ as zeolite is slurried in water at a ratio of 25-50:1 water tozeolite. The exchange solution is heated at 95 C. for 2 hours and thenfiltered. This procedure can be repeated up to three times. Followingthe final exchange, the zeolite is washed several times with water anddried. This NH₄ ⁺ form of SSZ-53 can then be converted to the H⁺ form bycalcination (as described in Example 9) to 540 C.

Example 13

N₂ Micropore Volume

The H⁺ form of the products of Example 2 after a treatment as inexamples 9, 10 and 12 was subjected to a surface area and microporevolume analysis using N₂ as adsorbate and via the BET method. Thesurface area of the zeolitic material is 416 m²/g and the microporevolume is 0.17 cc/g, thus exhibiting considerable void volume.

Example 14

Constraint Index Determination

The hydrogen form of the Al-SSZ-53 zeolite of Example 2 (after treatmentaccording to Examples 9, 10, and 12) was pelletized at 2-3 KPSI, crushedand meshed to 20-40, and then >0.50 gram was calcined at about 540 C. inair for four hours and cooled in a desiccator. A 0.56 g sample waspacked into a ¼″ OD stainless steel tube with alundum on both sides ofthe zeolite bed. A Lindburg furnace was used to heat the reactor tube.Helium was introduced into the reactor tube at 9.4 cc/min andatmospheric pressure. The reactor was heated to about 427 C., and a50/50 (w/w) feed of n-hexane and 3-methylpentane was introduced into thereactor at a rate of 8 l/min. Feed delivery was made via an ISCO pump.Direct sampling into a gas chromatograph begins after 10 minutes of feedintroduction. The Constraint Index value was calculated from the gaschromatographic data using methods known in the art, and was found to be0.73. At 427 C. and 10 minutes on-stream, feed conversion was >99%. At40 minutes the conversion was 64%. At 70 minutes it was 36% and at 100minutes it was 22%.

SSZ-53 has very high cracking activity, indicative of strongly acidicsites. In addition, the catalyst has good stability. The C.I. of 0.73shows almost no preference for cracking the branched alkane(3-methylpentane) over the linear n-hexane, which is behavior typical oflarge-pore zeolites.

Example 15

Hydrocracking of n-Hexadecane

The product of Examples 5 was treated as in Examples 9, 10, and 12. Thena sample was slurried in water and the pH of the slurry was adjusted toa pH of ˜10 with dilute ammonium hydroxide. To the slurry was added asolution of Pd(NH₃)₄(NO₃)₂ at a concentration which would provide 0.5wt. % Pd with respect to the dry weight of the zeolite sample if all thePd exchanges onto the zeolite. This slurry was stirred for 48 hours atroom temperature. After cooling, the slurry was filtered through a glassfrit, washed with de-ionized water, and dried at room temperature. Thecatalyst was then calcined slowly up to 900 F. in air and held there forthree hours.

The calcined catalyst was pelletized in a Carver Press and crushed toyield particles with a 20/40 mesh size range. Sized catalyst (0.5 g) waspacked into a ¼″ OD tubing reactor in a micro unit for n-hexadecanehydroconversion. Table X gives the run conditions and the products datafor the hydrocracking test on n-hexadecane. After the catalyst wastested with n-hexadecane, it was titrated using a solution of butylamine in hexane. The temperature was increased and the conversion andproduct data evaluated again under titrated conditions. The resultsshown in Table X show that SSZ-53 is effective as a hydrocrackingcatalyst.

TABLE X Temperature 276° C. (528 F.) 303° C. (578 F.) Time-on-Stream(hrs.) 97.8-101.3 167.6-170.1 WHSV 1.55 1.55 PSIG 1200 1200 Titrated? NoYes n-16, % Conversion 93.4 92.3 Hydrocracking Conversion, % 70.7 70.5Isomerization Selectivity, % 18.2 22.4 Crack. Selectivity, % 81.90 77.6C₄−, % 12.0 12.3 C₅/C₄ 5.4 5.2 C₅ + C₆/C₅, % 29.67 28.97 DMB/MP 0.120.11 DMB/nC₆ 0.55 0.42 C₄-C₁₃ I/N 6.71 5.96

What is claimed is:
 1. A zeolite having a mole ratio greater than about20 of an oxide of a first tetravalent element to an oxide of a secondtetravalent element which is different from said first tetravalentelement, trivalent element, pentavalent element or mixture thereof andhaving, after calcination, the X-ray diffraction lines of Table II.
 2. Azeolite according to claim 1 wherein said zeolite is predominantly inthe hydrogen form.
 3. A zeolite according to claim 1 wherein saidzeolite is substantially free of acidity.
 4. A zeolite having a moleratio greater than about 20 of an oxide selected from the groupconsisting of silicon oxide, germanium oxide and mixtures thereof to anoxide selected from aluminum oxide, gallium oxide, iron oxide, boronoxide, titanium oxide, indium oxide, vanadium oxide and mixturesthereof, and having, after calcination, the X-ray diffraction lines ofTable II.
 5. A zeolite according to claim 4 wherein the oxides comprisesilicon oxide and aluminum oxide.
 6. A zeolite according to claim 4wherein the oxides comprise silicon oxide and boron oxide.
 7. A zeolitehaving a composition, as synthesized and in the anhydrous state, interms of mole ratios as follows: YO₂/W_(c)O_(d)  20-150 M_(2/n)/YO₂0.01-0.03 Q/YO₂ 0.02-0.05

wherein Y is silicon, germanium or a mixture thereof; W is aluminum,gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; cis 1 or 2; d is 2 when c is 1 or d is 3 or 5 when c is 2; M is an alkalimetal cation, alkaline earth metal cation or mixtures thereof; n is thevalence of M; and Q is at least oneN,N,N-trimethyl-1-phenylcycloalkylmethyl ammonium cation.
 8. A zeoliteaccording to claim 7 wherein W is aluminum and Y is silicon.
 9. Azeolite according to claim 7 wherein W is boron and Y is silicon.
 10. Azeolite according to claim 7 wherein Q has the following structure:


11. A method of preparing a crystalline material comprising an oxide ofa first tetravalent element and an oxide of a second tetravalent elementwhich is different from said first tetravalent element, trivalentelement, pentavalent element or mixture thereof, said method comprisingcontacting under crystallization conditions sources of said oxides and atemplating agent comprising a N,N,N-trimethyl-1-phenylcycloalkylmethylammonium cation.
 12. The method according to claim 11 wherein the firsttetravalent element is selected from the group consisting of silicon,germanium and combinations thereof.
 13. The method according to claim 11wherein the second tetravalent element, trivalent element or pentavalentelement is selected from the group consisting of aluminum, gallium,iron, boron, titanium, indium, vanadium and combinations thereof. 14.The method according to claim 13 wherein the second tetravalent elementor trivalent element is selected from the group consisting of aluminum,boron, titanium and combinations thereof.
 15. The method according toclaim 14 wherein the first tetravalent element is silicon.
 16. Themethod according to claim 11 wherein the templating agent has thefollowing structure:


17. The method of claim 11 wherein the crystalline material has, aftercalcination, the X-ray diffraction lines of Table II.